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MINIREVIEW

Self-assembly of conjugated oligomers and polymers at the interface: structure and properties
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Lirong Xu, Liu Yang and Shengbin Lei*

Received 14th January 2012, Accepted 1st May 2012 DOI: 10.1039/c2nr30122a In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of p-conjugated semiconducting oligomers and polymers, either at the solidair (including solidvacuum) or at the solidliquid interface. The structural aspects of the selfassembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the airsolid or liquidsolid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior signicantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to ne tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of conjugated oligomers and polymers. The information obtained could benet the understanding of the elements affecting the lm morphology and helps the optimization of device performance.

1. Introduction
p-Conjugated polymers and oligomers have attracted increasing attention because of their interesting structure, optical and electronic properties. In view of their potential applications in less expensive, so-called plastic optoelectronic devices, they are the most promising functional organic materials.14 Currently,
Key Laboratory of Microsystems and Microstructures Manufacturing, Ministry of Education, Harbin Institute of Technology, Harbin, 150080, P. R. China. E-mail: leisb@hit.edu.cn; Fax: +86 451 86403625; Tel: +86 451 86403625

thiophene-containing oligomers and polymers are receiving considerable attention due to their applications in electronic and optical devices, for example, eld-effect transistors (FETs),5 organic light-emitting diodes (OLEDs),6,7 molecular rectiers,8 organic thin lm transistors9,10 and other optical applications.11 Assembling structures of organic semiconductors are of essential importance to these devices where they are used as active layers.1214 One of the main technological attractions for such devices based on organic materials is that nearly all the functional layers can be deposited and patterned at low/room temperature by a combination of low-cost solution-processing and direct-write

Lirong Xu received her MS in 2011 from Gannan Normal University and is currently a PhD student in the Academy of Fundamental and Interdisciplinary Sciences at Harbin Institute of Technology. Her current research involves the synthesis of functional building blocks and characterization of their assembly at the solidliquid interfaces.
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Liu Yang is in her second year of Master degree in the Academy of Fundamental and Interdisciplinary Sciences at Harbin Institute of Technology. Her research is in the area of supramolecular assembly of conjugated oligomers.

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printing, which makes them ideally suited for the realization of low-cost, large-area electronic devices on exible substrates.15 In optoelectronic devices generally several interfaces are involved and the interfacial structure always plays an essential role in determining the performance of the devices. Not only the properties of individual molecules but also the conformation, orientation and packing structure of these molecules in the rst layer on the solid substrate can determine the nal properties of such optoelectronic devices.16 Therefore, understanding the properties of single molecules and the molecular arrangement at the interfaces is important in the fabrication of devices.1719 Characterization of the thin lm structure, especially within a few nanometer vicinity of the interface, is a challenging task because several interfaces are involved in this region, such as the solidsolid interface, the evolution layer from the interface to the bulk, and the solidair interface. These complex cases make it a tough task to fully characterize the interfacial structures and their evolution by conventional diffraction and microscopic techniques. Scanning probe microscopy, especially scanning tunneling microscopy (STM), is a powerful tool for investigating the self-assembled monolayers adsorbed onto solid substrates due to its high resolution. A scanning tunneling microscope also shows surprisingly good adaptability to different environments, it works well under ultrahigh vacuum (UHV), at the solidliquid interface and under ambient conditions. In this review, we will give a brief account on the recent scanning tunneling microscopy investigation of the interfacial structures and properties of p-conjugated semiconducting oligomers and polymers, either at the solidair (including solid vacuum) or at the solidliquid interface. The structural aspects of the self-assembly are highlighted, including the self-assembly of both oligomers and polymers, and a composite assembly formed with other functional building blocks.

Elena Mena-Osteritz et al.25,26 reported the self-assembling properties of p-conjugated oligothiophenes and cyclothiophenes. A series of molecules have been investigated by scanning tunneling microscopy under ambient conditions, and submolecular resolution STM images are obtained. The structures of dodecyl-substituted oligothiophenes (13), oligothiophenediacetylene (4) and cyclo[n]thiophene (5) are all shown in Scheme 1. Fig. 1 shows the corresponding STM images of the assemblies formed by the above compounds on the graphite surface. They can self-assemble at the solidliquid interface to form wellordered 2D structures. Both the linear p-conjugated oligomers 1

Scheme 1 Chemical structures of 15. (Reprinted with permission from ref. 26.)

2. Assembly of conjugated oligomers

2.1 Effect of the backbone structure Conjugated oligomers are promising optoelectronic materials due to their promising properties and processability. Their difference in chemical substitutions and backbones has different effects on the structure and properties. So far, p-conjugated oligomers which have been studied by STM at interfaces include oligothiophene,2022 oligo(phenylene ethynylene)23 and oligo(phenylenevinylene) derivatives.24

Shengbin Lei received his MS in 1999 from the Department of Chemistry, Shandong University and his PhD in 2002 in physical chemistry at the Institute of Chemistry, CAS (China) under the supervision of Prof. Chen Wang. After working for four years at the same institute in the eld of surface assembly and scanning tunneling microscopy, he joined the group of Prof. Steven De Feyter at K.U. Leuven as a postdoctoral researcher, working in the eld of 2D nanoporous networks and hostguest chemistry. He joined HIT in September 2009 as a professor. His current research focuses on 2D crystal engineering at interfaces and characterization of nanomaterials.
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Fig. 1 (a) Short-range ordering of the dodecyl substituted quaterthiophene 1 at the solutionHOPG interface (10 10 nm2, Vbias 500 mV, Iset 48 pA). The inset shows the underlying HOPG substrate (Vbias 20 mV, Iset 50 pA). (b) Long-range ordering of the decithiophene 2 at the solutionHOPG interface (90 90 nm2, Vbias 600 mV, Iset 32 pA). (c) STM image of the short-range ordering of head-to-tail coupled 3 on HOPG (20 20 nm2, Vbias 120 mV, Iset 5 pA). (d) The STM image of the long-range ordering of macrocycle 4 at the solutionHOPG interface (60 60 nm2, Vbias 542 mV, Iset 54 pA). The inset (bottom left) shows the underlying graphite. The second inset (top right) shows the STM image of an individual macrocycle overlaid with a theoretical calculated molecule. (e) Long-range ordering of the cyclo[12]thiophene 5 adsorbed on HOPG (28 28 nm2, Vbias 430 mV, Iset 24 pA). The inset shows the short-range ordering in detail (6.7 6.7 nm2, Vbias 430 mV, Iset 24 pA). (Reprinted with permission from ref. 26.)

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Scheme 3 Chemical structures of 4Ttm8T (8) and 4Ttm4T (9). (Reprinted with permission from ref. 28.)

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Scheme 2 Chemical structures of 6 and 7.

and 2 form a linear structure, but the packing is different due to the difference in the substituent pattern. Although in both cases the alkyl side chains are interdigitated to stabilize the assembly, the relative orientation of the side chains and backbones is different. For polymer 3, the packing between neighboring polymer chains is similar to oligomer 2 and the interdigitation of side chains results in an interchain distance determined by the length of side chains. The details of the assembling structure of polymers will be discussed later. The two cyclic oligomers spontaneously assemble at the solutionHOPG interface into a hexagonal pattern (Fig. 1d and e). The 2D lattice parameters of the assembling monolayer which corresponds to a sheet in the 3D bulk material agree very well with those obtained from X-ray analysis of single crystals, this suggests that STM can be a helpful tool to determine the packing arrangement of oligomers in the bulk especially when a single crystal suitable for X-ray analysis is not available. Wan Jun-Hua et al. have investigated the molecular packing structure in the self-assembled pn diblock and npn triblock heterostructure oligomers (6 and 7) which were based on thiophene and 1,3,4-oxadiazole.27 The structures of 6 and 7 are shown in Scheme 2. STM images of these two molecules obtained at the liquid HOPG interface are shown in Fig. 2. In the self-assembly of 6, there are many small ordered regions but no large uniform pattern can be observed, whereas the adlayer of 7 is uniform and well-ordered. The backbone of 6 is packed with head-to-tail mode, and the alkyl chains are possibly stacked with an

Fig. 2 (a) High-resolution STM image of the monolayer of 6 (11.9 11.9 nm2). (b) High-resolution STM image of the monolayer of 7 (15.6 15.6 nm2). (Reprinted with permission from ref. 27.)

interdigitated model. In contrast, oligomer 7 is clearly resolved with submolecular resolution and the monolayer structure is more ordered than that of oligomer 6. So the molecular backbone symmetry is expected to play an essential role in 2D selfassembly. Alkyl-substituted dual oligothiophenes, unsymmetrical quaterthiophene(4T)trimethylene(tm)octithiophene(8T) (8) and symmetrical 4Ttm4T (9) (Scheme 3), both molecules are linked by a trimethylene,28 were used to fabricate molecular monolayer structures on HOPG or Au(111) surfaces. STM observation shows that 8 forms both quasi-hexagonal and linear adlayers (Fig. 3). In the quasi-hexagonal adlayers, there are bright elliptical rings with dark depressions in the center. Each elliptical ring is composed of two 8 molecules. The linear adlayer is composed of short strands in a twisted conguration. Each strand is composed of two substrands and each substrand corresponds to one 8 molecule. STM images show that 9 which has a higher symmetry than 8 in its chemical structure forms both patterns with wave- and lamella-like appearance. In the wave-like adlayers, long-range ordering structures can be observed. Each strand consists of two substrands and each substrand corresponds to one 9 molecule. The lamellar adlayer has straight short sticks with a small black gap in the center of each stick, each stick corresponds to one 9 molecule, the central black gap was attributed to the trimethylene linker with low electron density (Fig. 4). Besides the oligothiophenes discussed above, self-assembly of p-conjugated oligo(p-phenylenevinylene) (OPV) dimers (10), tetramers (11) and hexamers (12) has also been investigated thoroughly.24 The structures of oligo(p-phenylenevinylene) (OPV) derivatives are shown in Scheme 4.29 STM experiments were carried out on oligo(p-phenylenevinylene) (OPV) derivatives at the 1,2,4-trichlorobenzene HOPG interface. Chiral oligomers 11 and 12 form chiral pure monolayers, while STM images show that achiral compound 10 forms enantiomorphous domains on the graphite surface. The molecular chirality is expressed in the orientation of the pconjugated backbone with respect to the propagation direction of the lamellae. A noticeable difference in STM images of 11 in comparison with those of 12 is the orientation of the molecules in the 2D self-assembled framework. While the packing of 12 seems to be determined by the p-conjugated backbones, the packing of the smaller 11 appears to be determined by the alkyl chains. So these results proved that even small differences in the molecular structures can have an essential impact on the self-assembling properties. These observations could be interesting for the construction of circularly polarized optoelectronic devices (Fig. 5).
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Fig. 3 STM images and models of 8. (a1) Large-scale STM image of the adlayer of 8 on HOPG in a quasi-hexagonal symmetry. (b1) High-resolution STM image of (a1). (c1) Structural model of the quasi-hexagonal adlayer. (a2) Large-scale STM image of the adlayer of 8 on HOPG in a linear pattern. (b2) High-resolution STM image of (a2). (c2) Proposed structural model of the linear adlayer. (Reprinted with permission from ref. 28.)

2.2 Effect of side chains It is conceivable that the amount and distribution of side chains attached to the molecular backbone have great effects on the 2D self-assembly process of conjugated molecules. Many investigations have shown that the interaction between alkyl side chains is important, sometimes even decisive to self-assembly.30,31 B auerle et al. used scanning tunneling microscopy (STM) to investigate b-alkylated oligothiophenes which have long alkyl side chains and observed that the formation of an ordered two-dimensional framework depends on the length of the oligothiophene backbone and the hydrocarbon chain.3234 Olga A. Guskova et al.35 have studied the self-assembly of b-alkylated oligothiophenes using atomistic molecular dynamics simulations, they compared the unsubsituted tetrathiophene (13) and the b-alkylated oligothiophenes including 3,3000 -dipropyl-quaterthiophene (14), 3,3000 dihexyl-quaterthiophene (15) (Scheme 5), and 3,3000 -didodecyl-

quaterthiophene (1) and they discovered that the presence of long alkyl side chains can induce a higher degree of order on graphite. The assembling properties of oligothiophenes were fundamentally due to the b-alkyl substitution pattern, only side chains longer than propyl can immobilize the molecule on the graphite surface to form ordered structures. It is well-known that the hydrogen bond plays an important role in the self-assemblies, so a series of oligothiophenes with carboxylic groups were synthesized in order to obtain a controllable molecular architecture. The chemical structures of these compounds are shown in Scheme 6.36 Although 16 has a carboxylic acid group which can form an intermolecular hydrogen bond, no long-range ordered adlayer of 16 could be formed, possibly due to the weak interaction between the thiophene backbone and the solid substrate. In the highresolution STM images, elliptical shaped features could be observed and every ellipse corresponds to a thiophene dimer.

Fig. 4 STM images and models of 9. (a1) Large-scale STM image of 9 on HOPG in a wave-like appearance. (b1) High-resolution STM image of (a1). (c1) Structural model of the wave-like adlayer. (a2) Large-scale STM image of 9 on HOPG in the lamellar pattern. (b2) High-resolution STM image of (a2). (c2) Structural model of the lamellar adlayer. (Reprinted with permission from ref. 28.)

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Scheme 4 The structures of the achiral OPV-dimer (10), the chiral OPV-tetramer (11) and OPV-hexamer (12). (Reprinted with permission from ref. 29.)

Instead molecule 17, which includes two carboxylic acid groups and two thiophene rings, forms long-range ordering. Through the hydrogen bonds between carboxyl groups, molecules initially connect with each other to form a molecular stripe, then organize into a 2D domain by the weak van der Waals interaction between the stripes. 18 has a more complicated asymmetric molecular structure, the large-scale STM image reveals three types of ordered packing geometries which were marked by A, B, and C. In A domains, the molecules form a rectangular structure through hydrogen bonds. In B domains, molecules form dimers which are connected by weak hydrogen bonds through the thiophene rings and alkyl side chains. In domain C, a L shape arrangement can be seen, every L consists of two 18 molecules, they interact with each other via hydrogen bonds between the end carboxylic groups. Molecule 19 can form a long-range ordered 2D framework. In one direction, the molecules form rows through the interdigitation of the alkyl side chains, and in the other direction, the molecules interact with hydrogen bonds between carboxylic groups (Fig. 6). The polar end groups attached to the conjugated backbone can inuence the self-assembling behavior because of dipole dipole interactions. Oligothiophenes substituted by one or two iodine atoms were investigated by scanning tunneling microscopy.37 The chemical structures and the corresponding STM images are shown in Fig. 7. An ordered monolayer of 1 was selfassembled at the liquidHOPG interface. The main driving force

for the arrangement is the van der Waals interactions between the interdigitated alkyl side chains. Iodinated quaterthiophene 20 can form self-assembled monolayers spontaneously. The thiophene backbone forms an angle of 23 3 with respect to the lamellar axis, this angle is smaller than that in the assembly of compound 1 (30 3 ). The oligothiophene backbones of diiodinated quaterthiophene 21 form an angle of 44 1 with respect to the lamellar axis. The difference in backbone orientation is attributed to the inuence of the iodine atoms on the assembling behavior. Gong Jian-Ru et al. have investigated the assembling structure of two alkoxy-substituted oligo(phenylene ethynylene)s (OPEs) which have similar structures (Fig. 8). They concluded that the different arrangement of the two molecules is due to the change of end groups.38 For molecule 22 the carboxyl groups possess a head-to-head conguration in the monolayer, and the hydrogen bond between neighboring carboxyl groups may contribute to the stability of the monolayer. Molecule 23 can form a less ordered monolayer when they adsorb on the surface of HOPG, the molecular orientation is also determined by the registered adsorption of alkoxy chains with respect to the substrate lattice, but due to the interdigitation of trimethylsilyl end groups, and they obtained a more closely packed structure. 2D assemblies of a series of alkoxy-substituted oligo(phenylene ethynylene)s (OPEs) with a longer backbone and various

Fig. 5 (a) STM image of 10 at the liquidgraphite interface, image size is 14.5 14.5 nm2. (b) STM image of 11 at the liquidgraphite interface, image size is 25.1 25.1 nm2. (c) Large scale image of 12 adlayer, image size is 50.0 50.0 nm2. (Reprinted with permission from ref. 29.)

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Scheme 5 Chemical structures of 1315. (Reprinted with permission from ref. 35.)

substituent patterns were also investigated by STM (Scheme 7). Through the intermolecular hydrogen bond, especially that between the carboxylic end groups, well-ordered assemblies were obtained.39 It was found that different end groups or a biethynylene linkage can change the 2D ordering signicantly (Fig. 9). Molecule 24 adsorbs on HOPG forming a stable monolayer, the alkyl chains are interdigitated between two adjacent bright stripes. Molecule 25 with two TMS end groups can also selfassemble into a well-ordered stable structure on HOPG. Within a row, adjacent molecules are dislocated with TMS groups interdigitated with each other. The different 2D ordering of molecules 24 and 25 arises from the number of TMS end groups. In molecule 26, the two TMS end groups are replaced by two

Fig. 6 (a) A large-scale image of 16 assembly on the HOPG surface, the upper right inset is the high-resolution STM image of 16. (b) Highresolution STM image of 17 assembled on HOPG. (c) STM top view of 18 assembly, A, B, and C indicate three domains. (d) The STM image of the assembly of 19, and a high-resolution image is shown in the inset. (Reprinted with permission from ref. 36.)

carboxyl groups. The two carboxyl groups of molecule 26 can form hydrogen bonds with carboxyl groups of adjacent molecules. Molecule 27 forms a monolayer which contains many domains. In the STM image, each molecular backbone dislocates in the same stripe, biethynylene provides enough space for the alkyl chains to interdigitate with those from the neighboring rows. Due to the formation of hydrogen bonds, molecule 28 forms a similar monolayer as molecule 27 but without dislocation. In comparison with molecules 25 and 26, the presence of a biethynylene group in molecules 27 and 28 changes the distance between neighboring alkyl chains along the backbone and in turn changes the intermolecular interaction and tunes the 2D assembling structure. 2.3 Edge-on against face-on, the effect of p stacking In order to maximize the moleculesubstrate interaction in most cases aromatic molecules tend to adsorb with their molecular plane parallel to the substrate surface, resulting in a face-on conguration as shown in the results mentioned above. Even for molecules that exhibit quite strong tendency of intermolecular p stacking, for instance tetrathiafulvalene (TTF), other kinds of non-covalent interactions such as hydrogen bonding are still necessary to force the molecule to adopt an edge-on conguration so that intermolecular pp stacking becomes possible. Puigmart -Luis et al. have developed a strategy to introduce Hbond forming amide groups into the side chains of TTF and found out that the cis constitutional isomers form well dened supramolecular bres at the solidliquid interface with the TTF unit tilted with respect to the substrate surface.40 Scanning tunneling spectroscopy proved the decrease of the conductance gap due to the intermolecular pp stacking. Even multilayers with parallel or
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Scheme 6 Structures of 3-thiophene acetic acid (16), 2,20 -dithiophene5,50 -dicarboxylic acid (17), 30 -pentyl-5,20 :50 ,200 -terthiophene-2,500 -dicarboxylic acid (18), 40 ,300 -dipentyl-5,20 :50 ,200 :500 ,2000 -quaterthiophene-2,5000 dicarboxylic acid (19). (Reprinted with permission from ref. 36.)

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Fig. 7 A comparison of packing patterns observed for compounds 1, 20 and 21. Left, STM image of 1: 16.4 16.4 nm2; middle, STM image of 20: 22.6 22.6 nm2; right, STM image of 21: 19.2 19.2 nm2. The parameters (a, b, and a) of the unit cells of the three derivatives are provided, as well as the angle between the molecular axis and the lamellar axis (g) and the density of molecules in the monolayer (M nm2). (Reprinted with permission from ref. 37.)

cross-conguration of these supramolecular bres can be stabilized with the aid of intermolecular hydrogen bonds which opens the possibility to interconnect these nanowires.41,42 Noncovalently or covalently connected multiporphyrin arrays represent both ideal models for the study of the energy transfer mechanism and potential functional components in nanodevices. Porphyrin hexamers covalently connected to a benzene ring were synthesized and STM investigations revealed that the uncoordinated molecule 29 forms kinetically favored face-on oriented structures at the 1-phenyloctaneHOPG interface, which gradually changes to a more thermodynamically favored lamellar phase.43 The intermolecular distance measured from the submolecularly resolved images suggests that molecule 29 adopts an edge-on orientation in the lamellar phase, which is stabilized by intermolecular pp stacking. The zinc coordinated

compound 30 forms exclusively a lamellar assembly without formation of a kinetically favored face-on orientation due to the increased pp interactions between the molecules of 30. The orientation of 30 in the assembly can be further manipulated by the addition of a potential axial ligand of zinc. The addition of a small bidentate ligand diaza[2,2,2]bicyclooctane (DABCO) further stabilizes the lamellar phase by coordination to the ZnII ions while still preserving the pp stacking between porphyrin units (Fig. 10b). However, addition of a larger ligand, 4,40 bipyridine, disrupts the pp stacking, leading to the exclusive formation of a face-on structure, which highlights the importance of pp stacking in stabilizing the columnar structure. Even larger porphyrin oligomers, dodecamers, show a similar assembling behavior at the solidliquid interface.44 The metal free dodecamer 31 forms uniform large lamellar domains with edge-on orientation (Fig. 10c). Despite their large diameter, individual dodecamers can be clearly distinguished. Possibly due to the axial coordination of water molecules the zinc coordinated dodecamer 32 did not form stable adlayers. Only after addition of excess DABCO ligands instantaneous formation of stable lamellae was observed. The precise control between edge-on and face-on orientations by addition of appropriate ligands is of great interest considering the application of such porphyrin oligomers in nanodevices. 2.4 Composite structures Most studies on binary mixtures show phase separation or formation of randomly mixed monolayers. It remains a challenge to control the ordering of multi-component mixtures at the molecular level.4548 Mohamed M. S. et al.37 have used scanning tunneling microscopy to investigate mixtures of three quaterthiophene
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Fig. 8 (a) The chemical structure of molecule 22 and the corresponding large scale STM image. (b) A large scale STM image of molecule 23, the chemical structures of molecules 22 and 23 are shown on top of the STM images. (Reprinted with permission from ref. 38.)

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Scheme 7 Chemical structures of alkoxy-substituted oligo(phenylene ethynylene)s 2428. (Reprinted with permission from ref. 39.)

derivatives at the liquidsolid interface. The chemical structures of these compounds are shown in Fig. 7. The mixture of molecules 1 and 20 predominantly shows a monolayer of 1 even at a ratio of 1 : 10, only at much higher ratios molecule 20 can form monolayers at the liquidsolid interface. For mixtures of molecules 1 and 21, only monolayers of molecule 21 were observed at the ratio of 5 : 1. This consequence is related to the packing density of each compound. The self-assembly of oligo(phenylene ethynylene) (OPE) (29) can be used as a molecular template; organic molecules such as coronene (COR) and biomolecules such as tripeptides are controllably monodispersed on HOPG by using this template49 (Fig. 11). At a 1 : 2 molar ratio of COR to 33, each cavity of the network of 33 is occupied by a single COR molecule (Fig. 11b). COR molecules are not clearly resolved due to the movement of the COR molecules in the slightly larger cavity compared to its

size. At a molar ratio of 1 : 1 of COR to 33, CORs form a dimer in each cavity, and COR molecules are well stabilized in the framework. At a 3 : 2 molar ratio, as marked by arrows I and II in the image (Fig. 11d), there are two types of COR molecular arrays, single COR molecule and COR dimer, which ll within the space of 33 template in arrays I and II, respectively. At this ratio, COR not only lls the cavities adjacent to the carboxyl groups but also those close to the ethynylene end groups. These results illustrate that COR molecules can be distributed in a controlled fashion in the 33 template by tuning the concentration ratio. Oligopeptide TGG can also be dispersed within the 33 template. Additionally, molecule 34 and its coadsorption with C18H37Br are studied by scanning tunneling microscopy on HOPG50 (Fig. 12). Molecule 34 can self-assemble into ordered helix structures by itself, but coadsorption with C18H37Br resulted in

Fig. 9 The high-resolution STM images of molecules 24 (a), 25 (b), 26 (c), 27 (d) and 28 (e). (Reprinted with permission from ref. 39.)

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Fig. 10 (a) Structures of compounds 2932. (b) High resolution STM image of a domain of edge-on oriented 30 and DABCO on graphite. Cartoon demonstrating that the addition of DABCO results in a welldened columnar structure by bridging adjacent 30 molecules is shown below. (c) STM topography of a monolayer of 31 at the phenyloctane graphite interface. The inset shows a high resolution image of the columnar structure. (Reprinted with permission from ref. 43 and 44.)

the bicomponent lamellar structure. The bright rods were attributed to the backbones of 34. The bicomponent cocrystal is stabilized by the van der Waals interaction and the halogen bonding between 34 and C18H37Br. Elena Mena-Osteritz and B auerle have investigated the complexation of C60 on a cyclothiophene monolayer.51 Chemical structures of cyclothiophene (35) and C60 are shown in Scheme 8. Molecule 35 can self-assemble into a highly ordered monolayer of a hexagonally packed framework. When deposited onto the macrocycle template from a 1,2,4-trichlorobenzene solution C60 can interact with the p-system of the macrocycle and selfassemble into a second layer on top of the 35 template (Fig. 13). At a very low coverage, only a few C60 adsorb in the cavities of the macrocycle template at different sites. At high coverage, C60 interacts with the 35 molecular template at precisely the same location and forms nearly perfect domains.

3. Assembling of conjugated polymers

3.1 Polythiophene Poly(3-alkylthiophene)s (P3ATs) were used as active components in eld effect transistors (FETs), light-emitting diodes (LEDs) and photovoltaic devices. The control of the structural order on the molecular level has important consequences on the electronic properties. X-ray diffraction (XRD) studies of a solution-processed lm of P3ATs reveal lamellar structures with 2D sheets resulting from interchain stacking. Crystalline domains
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with a typical size of 10 nm were deduced from XRD.52,53 Within these ordered domains, the thiophene rings were deduced to adopt an all-trans conformation, while it is also reasonable that polymer folds occur between these crystalline domains and form a disordered/amorphous matrix. However, concerning the polymer conformations within the folds there is very limited information available due to the lack of appropriate techniques to study these folded conformations at the atomic level. In this sense, STM and P3ATs represent a perfect model system for the investigation of conformations of folded polymer chains considering the atomic resolution of STM and the good conductivity of P3AT. In one of the pioneer works by MenaOsteritz et al.,54 STM was used to study the assembly of head-totail coupled poly(3-alkylthiophene)s (HT-P3ATs) at the solutionHOPG interface. The compounds investigated, HTcoupled poly(3-hexylthiophene) (P3HT) and HT-coupled poly(3-dodecylthiophene) (P3DT), comprised high regioregularities of 95% and 98%, respectively. STM images reveal a long range order on the micrometer scale with molecularly resolved individual strands. Ordered domains are oriented according to the three crystallographic axes of the HOPG substrate. The side chains prefer to adsorb with fully extended and interdigitated fashion along the main graphite axes. In most of the surface, the conjugated backbones are linearly arranged with the thiophene repeating units adopting an all-trans conformation. However, a closer look at the images reveals that chain folding also occurs in the monolayer, in which cis conformations of the thiophene units are a prerequisite for the fold (Fig. 14). Hair-pin folds, where the polymer chain change their propogate direction for 180 within a few repeating units, are regularly seen. The calculation supported analysis of the folds in both polymers reveals that an intramolecular hair-pin fold is composed of seven thiophene units in a cis conformation in the case of P3HT and eight units for P3DT. Thanks to the atomic resolution of STM images,  periodicity can be determined in the dodecyl-substituted a 6.8 A P3DT chains, which corresponds to a compressed bithiophene repeating unit (in the gas phase the length of a bithiophene unit is  This signicant compression was calculated to be 7.4 A). attributed to the epitaxial effects of the underlying substrate surface on the alkyl side chains. The submolecular resolution of STM also allows for the determination of interchain distances in  and 1920 A  for P3HT the lamellae. Typical distances of 1314 A and P3DT were found, respectively. These values agree well with semiempirical calculations with the hexyl and dodecyl side chains fully interdigitated, but smaller than that determined from XRD measurements. This difference was attributed to the epitaxial effects of the graphite surface which promote the interdigitation between side chains in order to maximize the intermolecular interactions. The submolecular resolution of STM images also facilitated the measurement of the polymer chain contour length, which allows the determination of the number of repeating units in individual strands. However, the average degree of polymerization estimated from STM images is lower than those from GPC and MALDI-TOF. Though XRD studies revealed a lamellar structure with 2D sheets resulting from interchain stacking in the solution processed lms, despite the occurrence of self-organization in some areas, the global microstructure of P3HT lms should not be
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Fig. 11 (a) Chemical structures of 33 and COR. (b) High-resolution STM image of one-by-one distribution of COR. (c) High-resolution STM image of two-by-two distribution of COR. (d) High-resolution STM image of one-by-two distribution of COR. (Reprinted with permission from ref. 49.)

regarded as simply polycrystalline. Instead, one should rather expect polycrystalline domains embedded in a disordered/ amorphous matrix. STM studies on self-assembled P3HT dry lms cast from chloroform to an HOPG surface proved this hypothesis.55,56 Polycrystalline domains were observed to coexist with disordered/amorphous polymers, which partially cover the surface and prevent clear observation of the underlying substrate. Monodomains were observed to be interconnected by folded chains. These monodomains follow the three-fold symmetry of the HOPG substrate due to the epitaxial effects. However, domains with a small mist angle of 5 were also observed. The chain-to-chain distance in the crystalline domains was determined to be 1.40 0.05 nm, which corresponds well with a full interdigitation of hexyl side chains. This value is in good agreement with STM measurements at the solutionsubstrate interface while signicantly smaller than 1.6 nm from XRD measurements in bulk samples. The domain size in the transverse direction (perpendicular to the conjugated backbone) can be determined from the full width at half maximum (FWHM) of the FFT peaks. The value deduced (18 2 nm) is in very good agreement with that determined from the direct space. The domain size in the parallel (along the conjugated backbone) direction, which is not accessible by other techniques, can be estimated directly from the STM images, and an average size of 20 nm is revealed. This veried that STM is a powerful tool for studying the mesoscopic ordering of conjugated polymers.
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Similar to that at the solidliquid interface, chain folding occurring with angles of 120 , 60 and 180 was observed. Another interesting feature is that since the mono-domains with different orientations are interconnected by folded chains, the frontiers between domains cannot be precisely dened, thus the concept of grain boundary is not totally adequate for describing P3HT lms. Inclusion of carbon nanotubes can increase the effective crystallinity of conjugated polymers, and this kind of composite materials was proved to be promising for use in organic photovoltaic and optoelectronic memory devices. Thus the way by which the polymers are attached to carbon nanotubes becomes an interesting topic of research. Goh et al. have carried out STM investigations on the effect of the substrate curvature on the adsorption of P3HT on single walled carbon nanotubes (SWCNTs).57 A SWCNT with a diameter of 1.4 nm was used in their study. Rod like features with lengths ranging from tens to 200 nm were observed in the STM images, and the diameter of these features was determined to be 2.1 to 2.5 nm, which is in good agreement if assuming a 0.38 nm stacking distance of the polymers and taking into account the van der Waals radius of the polymer. Besides the diameter, high resolution STM images also revealed a high degree of P3HT chain organization along the entire tube axis. The cross-section measurement along the axis reveals an average periodicity of 1.68 0.02 nm, substantially larger than the polymer chain-to-chain distance of 1.45 nm found on HOPG, which may indicate that the substrate curvature plays
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Fig. 12 Large-scale (a) and high-resolution (b) STM images of the selfassembly of 34/C18H37Br on HOPG. (c) High-resolution STM image of C18H37Br with a head-to-head conguration on HOPG. (d) Structural model of the adlayer in (b). The chemical structures of 34 and C18H37Br are overlaid on top of the STM images. (Reprinted with permission from ref. 50.)

Scheme 8 Chemical structures of 35 and C60. (Reprinted with permission from ref. 51.)

a fundamental role in the assembly of ordered domains. A chiral angle was also revealed for the polymer chains in wrapping the nanotubes, which may indicate that at least for the P3HT SWCNT composite the chirality of CNTs could signicantly inuence the polymer structures deposited at the surface. The adsorption of P3HT has also been investigated on other substrates. Terada et al. deposited P3HT on a H-terminated Si(100) surface using a pulse-injection method.58 This method provides a way to deposit large molecules with high molecular weight and produce contaminant-free surfaces by avoiding direct exposure of the substrate to air during preparation. Polymers were adsorbed as isolated species on the surface with no packing features or self-assembly (Fig. 15). The contour length could be precisely determined. Chain folds were usually observed along the polymer chains and the linear strands between folds comprise an almost all-trans conformation of the repeating units. The average length of the linear strands was 17.2 nm. The relatively large length of extended conformation was attributed to the highly rigid character of the P3HT backbone because of the steric hindrance of hexyl side chains. The isolated polymer molecules observed in this study are in contrast to the XRD and STM results on the solution processed lms where self-assembly of P3HTs was conrmed. The absence of self-assembly could be due to the rapid vaporization of the chloroform solvent. In another work, Kasai et al. have used the same pulse-injection method to deposit P3HT on the Cu(111) surface.59 STM images reveal also isolated polymer chains, however, on the Cu(111) surface P3HT chains adsorb with majority being in rigid all trans conformation, coexisting with 60 or 120 folds, which are composed of ve or three thiophene rings with continuous cis conformation. The number of monomer units in one polymer chain can be denitely counted, allowing the determination of the absolute molecular weight of the polymer. Besides imaging, the spectroscopic mode, scanning tunneling spectroscopy (STS) provides a powerful tool for detecting the local electronic states, especially when combined with the imaging mode, it provides a powerful tool to investigate, at the local scale, the precise relationship between the structural organization and electronic properties. The simultaneous acquisition of STM topographic and 2D spectroscopic images should allow the investigation of the impact of the polymer local conformation on its electronic properties. For this purpose, Scifo et al.60 have investigated the local electronic properties of the selforganized 2D polycrystals of poly(3-dodecylthiophene) (P3DT)

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Fig. 13 (a) STM image of a monolayer of 35 on HOPG, including a 35C60 complex (white arrow), image area: 11.6 8.7 nm2. (b) STM image of a monolayer of 35 on HOPG and C60-fullerenes adsorbed at different sites, image area: 20 20 nm2. (c) STM image of 35C60 complexes, including some non-complexed macrocycles (deep red) and different domains (A, A0 and B), image area: 79 79 nm2. (Reprinted with permission from ref. 51.)

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polymer chains adsorbed as a second layer were also occasionally observed, which enables the investigation of the contribution of pp electronic coupling on the STS spectra and images. Most of the P3DT chains in the second layer were randomly oriented, crossing the underlying chains in the rst layer. The chains in the rst and second layers show an apparent height of 0.24 0.04 nm and 0.29 0.05 nm, respectively. The difference in apparent height between the rst and second layers could be a result of the variation of electronic properties above the two layers, with a greater electronic density above the second layer chains compensated by an increased tipsample distance. STS gives more information on the local electronic effects. Current imaging tunneling spectroscopy (CITS) images give a sharp contrast within a broad energy range due to the different electronic properties between the HOPG substrate and the polymer assembly. Both IV curves and conductance spectra of the polymers exhibit an extended plateau and both are asymmetric: a much higher current was obtained for positive than for negative bias (Fig. 16). The STS conductance gap was attributed to the HOMOLUMO band gap and simulations with ab initio density functional theory were conducted to further conrm the nature of the STS conductance gap. Based on the simulation, no signicant charge transfer should be expected. Although an increase of the HOMOLUMO gap over chain folds is expected, whatever the bias applied, CITS images show constant tunneling current over the polymer monolayer within statistical uctuation. This means at room temperature the electronic properties of a single chain are weakly affected by the folding. However, CITS images recorded over chains of the second layer above +0.6 eV show a remarkable contrast, which arises from the 0.3 eV shift of the HOMO edge as shown in

Fig. 14 Chemical structures of P3HT, P3DT and the corresponding STM images. (Reprinted with permission from ref. 54.)

drop-cast from CHCl3 solution to a HOPG surface. STM and STS measurements were conducted under UHV conditions at room temperature. A typical STM image displays a highly organized 2D polycrystalline structure with oriented monodomains connected by well-dened regular chain folds. Isolated
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Fig. 15 STM images of pulse-injected regiorandom P3HTs at the Hterminated Si(100) surface, obtained at room temperature. Image size: (a) 150 150 nm2, (b) 43 43 nm2, (c) 70 70 nm2, and (d) 50 50 nm2. The inset in (d) shows a STM image of a clean H-terminated Si(100) surface. (Reprinted with permission from ref. 58.)

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Fig. 18 STM image of a polydispersed PPE at the phenyloctane graphite interface (Vbias 1.2 V, Iset 1.0 nA). (Reprinted with permission from ref. 62.)

Fig. 16 (a) Experimental and calculated IV spectra obtained over the bare substrate (HOPG), the rst polymer monolayer (P1) and the second polymer layer (P2). The calculated curves are shown in the inset. (b and c) Conductance dI/dV and normalized conductance spectra, respectively. The arrows point to the edges of HOMO and LUMO bands. (d) Topographic (top) and current images acquired during CITS measurements at different setting bias, 0.61 V (middle) and 0.86 V (bottom). The location of a chain fold is highlighted with white circles in the top and bottom images. (Reprinted with permission from ref. 60.)

especially developed dual-bias imaging technique the position of bromine end groups can be identied to be located in the center of two neighboring polymer strands, which conrms an end-toend model of the alkyl side chains in the monolayer of brominated P3ATs. This indicates that the polythiophene backbone of the second layer is systematically located on top of a row of bromine atoms, which suggests that the brominesulfur weak bondings are at the origin of a self-templating effect. This opens an avenue towards the designed self-assembly of conjugated polymers with 3D geometry. 3.2 Poly(phenyleneethynylene)s The self-assembly of p-conjugated macromolecules offers a strategy for the construction of well-dened nanometer structures with chemical functionalities and physical properties that are of potential use as active components in electronic devices. Among all the conjugated polymers, poly(p-phenyleneethynylene)s (PPEs) are of particular interest because of their rigid-rod structure, strongly anisotropic electronic properties, electroluminescence in the blue-green region and high and stable photoluminescence quantum yield. When deposited onto a HOPG surface from 1-phenyloctane STM reveals a nematiclike monolayer with both the conjugated skeletons and the hexyl side chains lying at on the basal plane of graphite (Fig. 18). The 2D Fourier transformation indicates that the conjugated skeletons are aligned according to the three-fold symmetry of the graphite substrate. The stiffness of the molecular rods and the low polydispersity play a key role in the formation of stable 2D structures. The distance between neighboring backbones was determined to be 1.62 0.10 nm, which is signicantly smaller than that expected from fully extended side chains. This indicates that the side chains are disordered between adjacent parallel backbones. In comparison, an oligomer composed of three PE units which has the same substituent skeletons forms a welldened 2D epitaxial crystal structure with an interchain distance of 1.46 0.10 nm. The difference in 2D structures of the oligomer and polydispersed polymer was attributed to the distribution of molecular lengths, which prevents the assembly of the macromolecules into perfect crystals. The time required for achieving a stable assembly is much longer for the polymer,
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Fig. 16b. This increase in the band gap for the second layer polymer chains was attributed to polarization effects. Although the rst layer forms relatively ordered arrangements, the upper layer of P3ATs merely forms a random pattern. For instance, in the case of P3DT a second layer constituted of isolated strands can be observed at the phenyloctaneHOPG interface, though most of these strands do not follow the direction of the underlying polythiophene backbones but rather intersect with random angles. However, when the alkyl side chains were brominated at the end, the brominated P3ATs form a clearly organized second layer, in which the polymer strands lie aligned following the direction of the rst layer and form parallel bundles (Fig. 17).61 Close inspection of the STM image indicates that the conjugated backbones are staggered. With the help of an

Fig. 17 Comparison of the self-assembly of P3DT (a) and brominated P3DT (b) at the phenyloctaneHOPG interface. (Reprinted with permission from ref. 61.)

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which is probably due to the self-segregation and consecutive adsorption that occurred at the molecular level at the interface.62 The PPE samples with different average lengths were also measured by SFM on a mica surface, where nanoribbons were detected for polymers with low molecular weight. In these nanoribbons the PPE molecules are oriented with their backbone parallel to the substrate. Statistics on the width of the nanoribbons yielded average values consistent with the molecular length expected, suggesting that the PPEs are packed parallel to each other with their long molecular axis perpendicular to the long ribbon axis. The mole-fraction distribution of molecular weight calculated from the ribbon width shows a very good agreement with that expected from the SchulzZimm distribution, which theoretically describes the molecular-weight distribution of polycondensation reaction. In comparison, the statistic of the contour length of adsorbed PPE molecules from STM images obtained at the HOPG1phenyloctane interface revealed that the experimentally determined maximum was shifted to higher rod lengths than that expected from the SchulzZimm distribution, indicating a favorite adsorption of the elongated molecules. Also, the experimental histograms are narrower than the SchulzZimm plots, which suggest molecular weight fractionation by the interface.63 The effect of substituents on the 2D assembling and chain folding of a series of PPE derivatives was studied at the solid liquid interface. However, different from the above reports, the

polymers were rst dissolved in toluene and then after solvent evaporation a drop of 1-phenyloctane was added before STM imaging. In this way, submolecularly resolved STM images were obtained, which reveal diverse forms of chain folding in the assembling monolayer.64 The results demonstrate that the structure and concentration of side chains affect not only the supramolecular order at the interface but also the chain folding characteristics in the adsorbed layer. The degree of polymerization and molecular weight distribution were directly determined by analysis of the contour length of polymer chains. The distribution of the polymer contour length agrees quite well with that expected from the SchulzZimm distribution and no fractionation was observed. This differs from the observation of P. Samor et al.63 and can be attributed to the difference in the experimental protocol. These results demonstrate that STM provides a reasonable evaluation of the molecular weight distribution for a rigid-rod polymer. For such polymers, it is difcult to determine the correct molecular-weight distribution with standard analytical techniques such as gel permeation chromatography (GPC) due to the aggregation of polymer chains. The self-assembled monolayer of PPE could be used as a template to direct the assembly of other functional building blocks, for instance phthalocyanines. Coadsorption of PPE 1 with copper(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31Hphthalocyanine (CuPcBu8) yields a composite structure (Fig. 19). CuPcBu8 adsorbs commensurately atop PPE backbone, which leads to an increased intermolecular distance between CuPcBu8 molecules. The match of structural parameters between the template and subject plays an important role in the success of templating.65

Fig. 19 Molecular structures (top) and the composite assembly (bottom) of PPE 1 and CuPcBu8. The inset in the STM image is a schematic model of the composite assembly. (Reprinted with permission from ref. 65.)

Fig. 20 Diverse chain foldings observed in the PmPV adlayer. The corresponding molecular models of the polymer chains indicated by arrows in the images are also shown. (Reprinted with permission from ref. 67.)

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Fig. 21 (a) Structure of porphyrin oligomer and polymer. (b and c) STM images of the porphyrin polymer containing ca. 40 porphyrin subunits. (Reprinted with permission from ref. 70.)

3.3 Poly[(m-phenylenevinylene)-co-(2,5-dioctoxy-pphenylenevinylene)] (PmPV) PmPV is a semi-conjugated luminescent polymer whose structure is a variation of the more common poly(p-phenylenevinylene) (PPV) and has been used to form composites with carbon nanotubes for photovoltaic devices.66 Thus the interfacial structure and interaction modes of PmPV with carbon nanotubes are of fundamental and technological interest. Due to the structural similarity PmPV/HOPG was used as a model system.67 Submolecularly resolved STM images reveal that PmPV tends to adsorb straight on the HOPG surface with its backbone parallel to the surface. Small ordered domains can frequently be detected within which the PmPV chains are packed parallel to each other with the alkyl side chain interdigitated. The exibility of the semi-conjugated PmPV backbone results in a high frequency of chain folding with the 60 , 120 and 180 (hairpin) folds as the basic modes (Fig. 20). The orientation of the PmPV chains is determined by the registered adsorption of the semiconjugated backbone and alkyl side chain with the underlying substrate lattice. The planar adsorption conformation of the conjugated backbone of PmPV allows strong overlap of the highly delocalized electron system of the substrate with the pelectrons of the PmPV backbone. This is in agreement with the theoretical simulation on PmPV/SWNTs in which PmPV adsorbs onto nanotubes with a planar conformation along the axis of the nanotube. In photovoltaic devices, PPV derivatives are commonly mixed with C60 derivatives to form heterojunctions, which is quite important in order to improve the performance of devices. The interfacial structure of such composites prepared by the electrochemical method was studied by in situ EC-STM on a Cu(111) surface. The composite lm was prepared by sequential adsorption of an oppositely charged poly{(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene)-alt-1,4(2,5-bis(2-(2-hydroxylethoxy)ethoxy))phenylenevinylene} (BHPPV) and hexa(sulfobutyl)C60 (HSC60), which result in a 4 3O3 adlayer. The density of this adlayer is higher than that formed by pure BH-PPV (4 4O3) and is also different from that of HSC60 (4 4).68 Another approach to the preparation of the heterojunctions involves the application of preferential adsorption. When a 1 : 1 mixture of PmPV and copper(II) 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (CuPcOC8) was applied onto the basal plane of graphite, PmPV adsorbs preferentially onto the surface due to its higher afnity, while in the upper layer these two compounds phase segregated into different domains.
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In this way, a vertical heterojunction could be created in the sequence of graphitePmPVCuPcOC8.69 The combined characterization with STM and AFM gives out detailed information on the interfacial structure of the composite lm, which could be very important for understanding the mechanism of OPV and OFET devices and also for the improvement of their performance. 3.4 Other polymers Conjugated oligo and polyporphyrins are of great interest due to their potential applications in nonlinear optics and light harvesting. Like other polymers, the interfacial properties of these materials also play an important role in their applications in molecular electronics. P. H. Beton et al. have used the UHV electrospray deposition (UHV-ESD) method to prepare the monolayer of oligo- and polyporphyrins directly from solution.70 Surprisingly despite their large size, the porphyrin oligomers (hexamer) can diffuse on the surface and form highly ordered islands, and the porphyrin units can be clearly resolved. The 2.6 0.2 nm intermolecular distance indicates that the assembly of porphyrin hexamers is determined by side chain interdigitation. In contrast, the porphyrin polymer (contains ca. 40 porphyrin subunits) forms small quasi-close-packed regions where chains are parallelly aligned, coexisting with disordered regions (Fig. 21). In the disordered regions bends and kinks, even points where polymer chains across occur. The average polymer chain length determined from the STM images (54 12 nm) agrees with that expected for a 40-unit chain. The angle between the axes of two crossing polymers is measured to be 91 9 , indicating that there is a preferred relative orientation for the overlapping of polymer chains. The authors have also determined the angular correlation length, Lc, which is a measure of the exibility of the polymer chains. The value of Lc (25 6 nm) is signicantly larger than the persistent length measured in solution, which possibly arises from the planar geometry of adsorbed molecules. The interactions with the surface and between neighboring molecules also contribute to the increase of rigidity. A similar phenomenon has also been observed for other polymers such as PPE, where the intermolecular interaction was found to signicantly inuence the folding of the polymer chains.64

4. Conclusions and perspectives

Conjugated oligomers can form well ordered supramolecular assemblies either at the airsolid or liquidsolid interface, thanks
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to the relatively high mobility and structural uniformity in comparison with polymers. The controllable preparation of wellordered nanoscale self-assemblies especially at the interface is the precondition for tailoring the performance of nano-devices. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior signicantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface and in turn optimize the performance of devices. The properties of plastic optoelectronic devices or functional organic materials depend on both the nature of the constituents of supramolecular assemblies and the interactions between them. Through tuning the non-covalent forces, supramolecular assemblies can be designed on purpose. Besides noncovalent interactions covalent interactions could be introduced to further stabilize the supramolecular structure and to improve the lifetime of nanoscale devices.71,72 For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of a long range ordered supramolecular assembly. Thus conjugated polymers normally only form small relatively ordered domains and between these domains chain foldings are frequently observed. Since the mono-domains with different orientations are interconnected by such folded chains, the frontiers between domains cannot be precisely dened, thus the concept of the grain boundary is not totally adequate for describing the assembled monolayers of conjugated polymers. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Diversity of folding modes was observed with submolecular resolution and structural models of these foldings were proposed based on the STM observation. The effect of chain folding on the electronic structure was also investigated by scanning tunneling spectroscopy. For conjugated polymers, it is difcult to determine the correct molecular-weight distribution with standard analytical techniques such as gel permeation chromatography (GPC) due to the aggregation of polymer chains. Besides the ability in studying the assembling structure at the interface, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by the statistic of the polymer contour length. Unlike GPC, which needs calibration via PPP or PS, the polymer contour length of individual polymer chains is measured directly from the STM images and no overestimation should be expected. However, one caution that needs to be kept in mind is that the molecular weight fractionation could happen at the solidliquid interface due to the stronger interaction with the substrate experienced by the larger molecules. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. Polymer monolayers with proper tailored structures were also used to template the assembling of other conjugated molecules such as phthalocyanine or self-template the growth of itself to form a controllable 3D assembly. These investigations open a new avenue to ne tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in
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the investigation of the assembling structures and properties of conjugated oligomers and polymers at the interface. The information obtained could benet the understanding of the elements affecting the lm morphology and help the optimization of device performance. STM has also proven its ability in the evaluation of the distribution of polymerization and true molecular weight, and can be applicable to other polymer systems. Although STM proved its usefulness in characterizing the interfacial structures of conjugated oligomers and polymers, there are severe limitations in using STM to investigate multilayer formation and that using several techniques would be desirable. The current investigations are mostly carried out on traditional STM substrates such as HOPG and metal single crystals, however, structural information on substrates such as ITO will be more helpful for the improvement of device performance. Graphene, which is an ideal candidate material for replacing ITO as the transparent conductive electrode in photovoltaic devices, will also be an interesting substrate.7375 Information on the interfacial structures and properties on such systems will directly help to understand the mechanism of related nanodevices.

Acknowledgements
This work is supported by the start-up funding of HIT, New Century Excellent Talents in University (NCET) from the Ministry of Education of P. R. China, the fundamental research funds for the central universities HIT.BRET2.2010002 and the National Science Foundation of China (21173061).

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